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以醋酸铜、间三氟甲基苯甲酸(m-TFBA)和邻菲咯啉(phen)为原料在甲醇水介质中通过水热反应,合成了一个新的单核铜髤配合物[Cu(m-TFBA)(phen)(H2O)2]·(m-TFBA),用元素分析、红外光谱和热重分析对配合物进行了表征。X-射线单晶衍射表明,配合物属三斜晶系,空间群P1,晶胞参数:a=1.00161(10)nm,b=1.15069(12)nm,c=1.28649(12)nm,α=82.217(2)°,β=84.767(2)°,γ=66.371(2)°,V=1.3448(2)nm3,Z=2,Dc=1.625g·cm-3,R1[I>2σ(I)]=0.0421,wR2[I>2σ(I)]=0.0958。铜(Ⅱ)分别与来自邻菲咯啉的2个氮原子、间三氟甲基苯甲酸的1个氧原子和2个水分子中的2个氧原子配位,形成变形的四方锥结构。配合物通过强的O-H…O氢键作用形成了二聚体结构,该二聚体又通过分子间弱的C-H…O氢键作用形成了一维链状结构。配合物中配位的间三氟甲基苯甲酸上的三氟甲基基团具有无序结构。对配合物中[Cu(m-TFBA)(phen)(H2O)2]+进行了量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。
A new mononuclear copper complex [Cu (superscript 2 +)] was synthesized by the hydrothermal reaction of copper acetate, m-TFBA and phen in aqueous methanol. m-TFBA) (phen) (H2O) 2] (m-TFBA). The complexes were characterized by elemental analysis, IR and TG analysis. X-ray single crystal diffraction showed that the complex belongs to the triclinic system with the space group P1. The unit cell parameters are a = 1.00161 (10) nm, b = 1.15069 (12) nm and c = 1.28649 82.217 (2) °, β = 84.767 (2) °, γ = 66.371 (2) °, V = 1.3448 (2) nm3, Z = 2 and Dc = 1.625 g · cm- )] = 0.0421, wR2 [I> 2σ (I)] = 0.0958. Copper (Ⅱ) complexes with two nitrogen atoms from orthophenanthroline, one oxygen atom from m-trifluoromethylbenzoic acid and two oxygen atoms from two water molecules to form a deformed tetragonal pyramidal structure. The complex forms a dimeric structure by a strong O-H ... O hydrogen bond, which in turn forms a one-dimensional chain structure via a weak C-H ... O hydrogen bond between molecules. The trifluoromethyl group on the m-trifluoromethylbenzoic acid complexed in the complex has a disordered structure. Quantum chemical ab initio calculations of [Cu (m-TFBA) (phen) (H2O) 2] + have been carried out to investigate the stability of complex, molecular orbital energies and some frontier molecular orbital compositional features.